Method for polymerization of vinyl compounds



United States Patent M 3,477,999 METHOD FOR POLYMERIZATION OF VINYLCOMPOUNDS Saburo Takeda, 29-24 Mitsuzawashimocho, Hirorni Higashi, andRyokichi Tarao, 44 Otsutomocho, Mikio Mizuno and Kazuyuki Watabe, 303Termaecho, all of Kanazawa-ku Yokohamashi, Kanagawa-ken, Japan, MichiakiSaito, 1938 Ookacho, Minami-ku, Yokohamashi, Kanagawa-ken, Japan, ShigeoNamikawa, 44 Otsutomocho, Kanazawa-ku, Yokohama-shi, Kanagawa-ken,Japan, and Takao Tsunoda, 28-15, 3-chome, Sataemachi, Tsurumi-ku,Yokohama-shi, Kanagawa-ken, Japan N0 Drawing. Filed Apr. 11, 1967, Ser.No. 629,916

Claims priority, application Japan, Apr. 11, 1966, 41/22,794; Sept. 30,1966, ll/64,536; Oct. 13, 1966, 41'/67,080; Oct. 22, 1966, 41/69,624;Dec. 29, 1966, 42/323; Jan. 10, 1967, 42/1,908

Int. Cl. C08g 1/56; B01j 11/84 US. Cl. 260-785 12 Claims ABSTRACT OF THEDISCLOSURE A method for polymerizing or copolymerizing vinyl chloride orvinylidene chloride which comprises polymerizing or copolymerizing saidcompound by the use of a modified Ziegler type catalyst consisting of atransition metal compound, an organoaluminum compound and a loweraliphatic alcohol possessing, as a substituent, an amino radical,nitrile radical or a halogen atom, the catalyst preferably consisting ofa transition metal compound and an isolated reaction product between anorganoaluminum compound and a lower alkanolamine.

This invention relates to a method for polymerizing vinyl compound. Moreparticularly it relates to a method for polymerizing vinyl chloride orvinylidene chloride or copolymerizing vinyl chloride or/ and vinylidenechlo- I ride in the presence of a modified Ziegler type catalyst.

It has been known that the polymerization of vinyl chloride orvinylidene chloride with a Ziegler type catalyst yields a coloredpolymer due to the dehydrochlorination of the formed polymer. In orderto overcome such a drawback, the use of various modified Ziegler typecatalysts have been studied. With regard to such studies, collectivereports are found in Vinyls and Polymers (Japan), vol. 5, No. 6, pp.2427 (1965) for vinyl chloride and A collection of lecture gists of the14th discussion assembly on high molecular compounds (Japan), pp.281-286 (1965) for vinylidene chloride. However it can hardly say thatanyone of the processes reported therein enables to overcome theabove-mentioned drawback satisfactorily. Accordingly, it is anobject ofthe present invention to provide a method for producing a non-coloredpolymer or copolymer of vinyl chloride or vinylidene chloride which doesnot accompany the dehydrochlorination. It is another object of thepresent invention to provide a method for producing the above-mentionedpolymer or copolymer having" a higher molecular weight by using acatalyst possessing a sufficiently high activity even at a relativelylow temperature which can be handled safely and affords a highpolymerization rate. It is a further object of the present invention toprovide a method for producing a 3,477,999 Patented Nov. 11, 1969powdery polymer which is rich in syndiotacticity and does not containtetrahydrofuran-insoluble part or other impurities. It is still afurther object of the present invention to provide a method forproducing a polymer which atfords a film superior in transparency. It isstill a further object of the present invention to provide a methodwhich can be applied to the copolymerization of vinyl chloride or/ andvinylidene chloride with a wide variety of polymerizable unsaturatedcompounds while affording a homw geneous copolymer containing hardly ahomopolymer.

These objects and other advantages can be attained by the method of thepresent invention.

According to the method of the present invention, a lower aliphaticalcohol containing an amino radical, nitrile radical and a halogen atomas a substituent, is used as a modifier of Ziegler type catalyst. Inother words the present invention consists in a method for polymerizingor copolymerizing a vinyl compound represented by a general formula ofwherein X is H or Cl atom, which comprises polymerizing orcopolymerizing said compound by the use of a modified Ziegler typecatalyst consisting of (a) a compound of transition metal, (b) anorganialuminum compound and (c) a lower aliphatic alcohol possessing theabove-mentioned substituent.

The compound of transition metal, which is a constituent of thecatalyst, includes halide, oxyhalide, alkoxide, alkoxyhalide,alkoxyacetylacetonate, acetoxyhalide or acetylacetonate of titanium,vanadium, chromium, iron, cobalt, nickel, zirconium or manganese.

Representative compounds are Ticl Tiel Ticl TiBr TiO(acac) Ti(ococH clVOCI Vcl Vcl Crcl CrO cl Cr(acac) Cocl Co(acac) Co(acac) Fe(acac)Fe(acac) Ni(acac) Zrcl Zrcl Zr(acac) acac is the abbreviation ofacetylacetonate radical. The material such as Ticl /a Alcl also isincluded. i

Illustrative oragnoaluminum compound includes compounds expressed by ageneral formula, AlRmX wherein R is alkyl, cycloalkyl or aryl radical, Xis halogen and m is 3, 2, 1.5 or 1 such as trimethyl aluminum, triethylaluminum, tricyclohexyl aluminum, triphenyl aluminum diethyl aluminumchloride, ethyl aluminum sesquichloride or ethyl aluminum dichloride.

The lower alcohol to be used in the present invention as a modifiercontains halogen atom, nitrile radical or amino radical. Exemplary loweralcohols containing halogen or nitrile are ethylene chlorohydrine,ethylene bromohydrine and ethylene cyanohydrine.

The lower alcohols containing amino radical are alkanolamine possessingN-substituted or non-substituted amino radical. As N-substitutedradical, N-alkyl, N-cycloalkyl, N-aryl radical are useful and one or twosubstitutions are possible.

As alkanolamines possessing N-substituted amino radical, monoethanolamines possessing, as N-substituent, one

3 or two radicals such as N-methyl, N, N-dimethyl, N-ethyl, N,N-diethyl, N-butyl, N, N-dibutyl, N-cyclohexyl, N, N-dicyclohexyl,N-phenyl, N, N-diphenyl or the like are illustrated.

As alkanolamine possessing non-substituted am no radical, mono-ethanolamine (MEA), n-propanol am ne (nPA), isopropanol amine (iPA),diethanolamine (DEA), triethanolamine (TEA) or the like are lllustrated.

Hydrochloric acid salts, and sulfuric acid salts of the above-mentionedalkanol amines are also useful.

In the polymerization, the above-mentioned three components (a), (b) and(c) can be added to the polymerization system as a mixed catalyst. It isalso possible to react an organoaluminum compound with a substitutedlower alcohol in advance and to use the isolated reaction producttogether with a compound of a transition metal, as a catalysts. In orderto attain the object of the present invention, the latter process ispreferable. Such reaction products of organoaluminum compound with asubstituted lower alcohol include reaction products consisting of AlMe-MEA (mol ratio 1:1), AlEt -MEA (1:1), AlEtg-HPA (1:1), AlEt -iPA (1:1),AlEt -MEA (1:2), AlEt -DEA (1: 1), AlEt -DEA (2:1), AlEt -(N-MeMEA) (1:1), AlEt -(N, N-Me MEA) (1: 1), AlEtg-(N-EtMEA) (1:1), AlEt -(N, N-EtMEA) (1:1), AlEt -(NPhMEA) (1:1), AlEt -(N, N-Ph MEA) (1:1), AlEt-(N-cyclohexyl MEA) (1:1), AlEt -(N, N-(cyclohexyl) MEA) With regard tothe mol ratio of these catalyst constituents, explanation is given inthe case where an alkanol amine is selected as a (cfconstituent.

First of all, the organoaluminum compound is used generally in a molratio of one or more relative to a compound of a transition metal. Whenan organoaluminum compound is used in the form of isolated reactionproduct with an alkanol amine, the mol ratio of said reaction productrelative to a compound of a transition metal is in the range of one ormore, preferably in the neighbourhood of one to three (Organoaluminumcompounds generally exist as a dimer but the mol ratio is calculated asmonomer throughout the specification and claims). It is also possible toadd free organoaluminum compound to the above-mentioned reaction productwith an alkanol amine. In such a case the activity of the resultantcatalyst increases further. However even in a mol ratio less than one,the catalysts possesses activity. For example when a reaction product ofAlEt -MEA (1:1) is used together with Ticl the catalyst having a zeromol ratio of Alcompound to Ti-compound, hardly shows activity but withthe increase of the ratio to 0.5, 1, 2, in this order, the activitygradually increases and reaches a maximum value in the neighbourhood of3 to 5. With the mol ratio greater than this value, the catalyticactivity does not increase but gradually decreases. Since the reactionproduct of AlEt -MEA possesses, by itself, a certain extent of catalyticactivity, the activity does not drop to zero even in a considerablyincreased mol ratio.

The mol ratio of organoaluminum compound to alkanolamine is selected inthe range where one is a central value. In the mixed catalyst systemwhere the abovementioned two constituents are used with a compound oftransition metal in the mixed form of the three, the mol ratio oftriethyl aluminum, diethyl aluminummonochloride or the like to alkanolamine is generally in the range of 1-4. Whereas when a reaction productof the two constituents is used, the organoaluminum compound is usedeven in the mol ratio less than one as in the case of the reactionproduct of AlEt -MEA (1 :2).

Since the catalysts system loses its actvity in the presence of water oroxygen, the reaction must be carried out generally in the atomosphere ofnitrogen. Though the reaction product of organoaluminum compound andalkanol amine decompose when exposed to the air, but it does not ignite.Compared with trialkyl aluminum which has a great ignition property, itaffords an advantage that it forms a stabilized catalyst system whichcan be handled safely.

The polymerization can be carried out even at a temperature generallyused in the polymerization with a common radical polymerizationcatalysts. However since the catalytic system of the present inventionis considerably stable to heat, it exhibits a suflicient catalystactivity even at a temperature of C. or more. The reaction is carriedout generally at 20 C. to 'C., preferably at 3070 C.

The reaction system shows grey, pale yellow or bright violet color anddoes not show black color as in the case of Ziegler type catalyst merelymodified with a common alcohol. When the catalyst activity is comparedby using the polymerization velocity as a barometer, the presentcatalytic system enables to complete the reaction in a time considerablyshorter than other catalytic systems. Namely, reaction proceedssutficiently in several to 10 hours with the present catalytic system.

The polymerization reaction is carried out in the presence or in thepractical absence of solvent. As a solvent to be used, a halogenatedhydrocarbon is preferred. For example, carbon tetrachloride, chloroform,tetrachloroethylene, trichloroethylene, 1,2-dichloroethylene,1,2-dichloroethane, amyl chloride, monochlorobenzene, monobromobenzene,dichlorobenzene or the like is used. Besides halogenated hydrocarbon,tetrahydrofuran, n-heptane dimethyl formamide, acetone, ethyl acetate,acetyl acetone or the like is also useful, but the yield is generallylower than the case where chlorinated hydrocarbon is used. Further whenvinyl chloride and vinylidene chloride is to be copoly-merized, one ofthem as a comonomer, itself, can be used also as a solvent to performsimultaneous function. If such a case is expressed by another way, it iscalled the case of non-solvent polymerization. Not only in the case ofcopolymerization reaction, such a non-solvent polymerization reactioncan be applied also to the case of homopolymerization. Since eachconstituent is prepared sometimes in a solution of n-hexane, tolune orthe like, the presence of such a small amount of solvent is consideredto belong to the non-solvent case where the presence of solvent issubstantially none. When compared with the solvent case, the non-solventcase has such advantages that since it does not use the solvent, thesolvent purification and recovery are unnecessary and the recovery ofunreaeted monomer is almost quantitative. Besides these, followingadvantages also are to be noted: the reaction proceeds smoothly even ata relatively low temperature, the polymerization speed is high, andresultant polymer is fine powder possessing high molecular weight whichhardly contains tetrahydrofuraninsoluble, easy in shaping films andafiords highly transparent films.

It has been proved that the vinyl polymer is not colored and showshardly any dehydrochlorination. This fact will be explained in the caseof polyvinyl chloride. When other types of Ziegler catalyst are used,the chlorine content of resultant polyvinyl chloride is usually lowerthan the theoretical value of 56.73%. This shows the occurrence ofdehydrochlorination. Whereas the chlorine content of the polyvinylchloride of the present invention is in the range of 55.656. 8% which isapproximately identical with the theoretical value. The ratio of theextinction degres at 638 cm.- and 690 cm." in the infra-red spectrum isused in the calculation of the degree of syndiotacticity. Since thisvalue is identical with or greater than the value of the polyvinylchloride obtained in the usual radical polymerization, it can be saidthat the polyvinyl chloride of the present invention is r'ichinsyndiotacticity. i

The present method can he applied not only to the homopolymerization ofvinyl chloride or vinylidene chloridebut also to the copolymerization.

Exemplary comonomers include vinyl compounds such as vinyl acetate,vinyl chloride (to vinylidene chloride), vinylidene chloride (to vinylchloride), styrenes such as styrene, alkyl vinyl ethers such as cetylvinyl ether, iso

The presence of comonomer constituent in the copolymer is detected bythe result of elementary analysis or infrared spectrum. Thecharacteristic point of the copolymerization reaction using the presentcatalyst system is to provide a homogeneous copolymer containing hardlyhomopolymers.

Following examples are given to illustrate the present invention butthey are by no means intended to limit the invention.

In each examples the indices apeparing immediately after the numbers ofexamples show the kind of monomer used; whether or not solvent is used,and the kind of catalyst used, in this order. The part in theparenthesis means that the isolated reaction product between thecomponents in the parenthesis is used together with the other componentoutside of the parenthesis, that is, a transition metal compound whichis abbreviated to M, here.

EXAMPLES 1-7 VC; non-solvent; M+ (AlEt -MEA) Various amounts of thereaction product of triethylaluminum and monoethanolamine (mol ratio1:1) (hereinafter referred to AlEt -MEA, the method for preparing thisproduct is disclose din the Japanese patent publication No. 2577/ 1967)and then 8.4 gr. of vinyl chloride monomer were charged to a reactiontube cooled at -78 C. in the atmosphere of nitrogen. Further, 0.5 ml. ofn-hexane solution of Ticl having a concentration of 0.607 millimole/ ml.(abs. amount of Ticl :0.303 millimole) was added to the mixture. Afterclosing the reaction tube by fusion, the polymerization was carried outat 30 C. for

24. hrs. under shaking.

The reaction system took gradually a suspension state showing greyishbrown to greyish yellow color. With the advancement of the reaction, thewhole system became almost immobile state. After completion of thereaction, the reaction tube was cooled again to 78 C. and opened. Then,reaction mixture was introduced in a large amount of methanol containinghydrochloric acid to precipitate white material, which was thenfiltered, washed with. methanol and dried. Resultant product was, ifnecessary, purified by reprecipitation from tetrahydrofuran andmethanol. The melting points of the products were measured. The analysisof chlorine was also carried out to confirm whether or notdehydrochlorination of the polymer had occurred. The infrared spectrumof powdery polymer in the region of 600 cm. to 800 cm. using KBr diskwas measured and the ratio of the optical densities at 638 cm.- and 690cm.- D638/D690, was calculated by way of base line method in order toinvestigate the syndiotacticity of the polymer. Results are listed inTable 1. In these Examples, the effect of the rnol ratio of: thecatalystconstituents (indicatedby the ratio of Al/Ti) on the yield andproperties of polymer was studied.

" TABLE 1 Polymer Product Yield o1 D638] M.P. (gr.) (percent) (percent)D690 C.)

6 The value D638/ D690 of the commercial polyvinyl chloride obtained bythe radical polymerization method was measured in the control run. Itwas 1.25.

EXAMPLES 8-19 VC; non-solvent; M+ (AlEt -alkanolamine) Hundred ml. ofvinyl chloride monomer was introduced in a 200 ml. pressure resistantglass reaction tube equipped with an electromagnetic stirrer, and twocopper pipes one of which was used for connecting to a vacuum source ornitrogen source o-r for introducing a monomer or a monomer mixture andthe other of which was used for connecting to a manometer or for purgingthe unreacted monomer, after the operations of connecting the tube tothe vacuum source then to the nitrogen source were repeated and the tubewas cooled to 20 C. Then, 1-2 ml. of toluene solution of the reactionproduct between triethyl aluminum and alkanolamine (1:1) and 1-2 ml. oftoluene solution of a compound of transition metal were introduced inthe reaction tube which was then closed. The polymerization was carriedout with vigorous agitation while maintaining the temperature of thebath of the reaction tube at 25-30 C. During the polymerization whichwas continued for one to several hours, the vapor pressure of vinylchloride monomer indicated always about 4 kg./cm. After the completionof the reaction, the unreacted monomer was discharged and the reactionproduct was dropped into methanol containing hydrochloric acid to beprecipitated. (If the precipitate was in the block form, it was choppedwith a Waring Blendor.) The precipitated reaction product, after beingleft to stand for over night, was washed with methanol, dried andweighed. If necessary, the polymer was purified by reprecipitation fromtetrahydrofuran and methanol. The mean polymerization degree of thepolymer was measured by the method shown in JllSK-6721 (1959). Namely,0.4 gr. of the polymer was dissolved in 100 ml. of nitrobenzene and therelative viscosity of the resultant solution was measured with anUbbelohde viscosimeter at 30 C. The mean polymerization degree of thepolymer was calculated from this value.

The reaction product of triethyl aluminum-alkanolamine had been preparedby the following process. [Triethylaluminum-isopropanolamine (1:1)reaction product] (abbreviated as AlEtgr-iPA) 3.27 gr. oftriethylaluminum was diluted with a mixture liquid of 8 ml. of n-hexaneand 4 ml. of toluene and the resultant solution was cooled to --78 C.2.2 ml. of isopropanolamine was gradually added. As in the case ofmonoethanolamine, thereaction product was treated to yield 2.56 gr. ofcolorless needle crystal. The product has asolubility to toluene, 0rn-hexane, greater than the reaction product between triethylaluminum andmonoethanolamine (1:1).

[Triethylalminum-n-propanolamine reaction product (1:1)] (AlEt -n-PA) Asin the case of isopropanolamine, the reaction product betweentriethylaluminum and n-propanolamine (3-amino-n-propanol), (1:1), wasprepared.

Isolated product was colorless plate crystal having a MP. of -92 C.Results are listed in Table 2. As'evident from the result, it can beseen that the meanpolymerization degree of the resultant polymer wasfairly high, and the catalyst activity is also sufiiciently highcompared with other catalystsyste-ms.

TABLE 2 Polymerization Polymer Transition Al/Ti ExampleAlEtg-alkanolamine reaction Metal (molar) Temp. Time Product 01 D638/M.P.

Number product (11111101.) Compound ratio) 0.) (hr.) (gr.) (percent)D690 0.) DP

8 AlEta-MEA, 5.00 2. 5 25 4. 5 22. 6 1. 66 1. 600 AlElZs-MEA, 4 75 3. 123 2. 22. 2 56. 6 1. 39 200-210 1. 600 AlEtg-MEA, 8 00..-. 4. 0 28 1. 018. 8 1. 59 172-177 1, 200 AlEta-nPA, 8.00..- 4. 0 30 5. 0 24. 8 1. 57175-180 1, 200 AlEta-iPA, 4 0 3. 0 23 2. 0 14. 9 56. 2 1. 48 190-200 1,700 AlEta-MEA HCl, 3.1 32 4. 6. 4 56. 7 1. 57 150-155 1. 900 AlEta-MEA,1 56 1. 0 30 1. 0 9.1 56. 5 l. 60 120-130 1, 580 AlEta-MEA 3 12.". 2. 030 1. 0 15. 9 56. 0 1. 62 122-130 1, 600 A1Et3-MEA,4 68 3.0 30 1.020.1 1. 53

AlEta-MEA 9 36 6.0 30 1.0 20. 0 1. 57 680 AlEta-MEA, 15.60. 10.0 30 1.018. 3 1. 40

19 AlEtg-MEA, 6.66 3. 0 30 1.0 24. 9 1.51

Ref. a AlEta," 4.68 V0013. 3.0 30 1. 0 1.0

Ref. b AlEtz, 4. VOGla 3. 0 30 1. 0 1.0

Ref. 0 AlEt2(OEt), 4.68. V001 3.0 30 1.0 4.0

Ref. (1 AlEtz(OEt), 4.68 V0013" 3. 0 30 1. 0 3. 7

9 H01 salt of monoethanolamine was used. b This aluminum compound wasnot crystalline but powdery.

The polymers obtained in the runs a and b were colored in pale yellow.

EXAMPLES -27 VC; non solvent; M+ (AlEt N-substitutedalkanolamine)Various amounts of triethyl aluminum was charged to 9 The experimentscarried out by the use of the catalyst described in U. Giannini, S.Cesca, Ghim. Ind. (Milan) 44, 371 (1962) and Belg. 611, 654 (Jan. 15,1962).

effected by the freezing point method using a benzene solution. Theresults are shown in Table 3.

TABLE 3 Al (percent) Et-group Mol. Wt.

N-substituted Alkanolamine Found Calcd. Found Calcd. Found Galcd.

Monoethanolamine 18. 41 18. 60 2. 0 2. 0 290 145. 2 N-methylethanolamine16. 94 16. 95 2. 0 2. 0 323 159. 2 N,N-dimethylethanolamine 15. 54 15.582. 0 2. 0 173. 2 N-ethylethanolamine 15. 13 15. 58 1. 8 2. 0 333 173. 2N,N-diethylethanolaminm-. 13. 31 13. 2.0 2. 0 408 201. 3N,N-dicyclohexylethanolamin 8. 83 8. 72 2. 2 2. 0 733 309. 5 N-phenylethanolamine 12. 07 12. 19 1. 8 2. 0 471 221. 3N,N-diphenylethanolamine. 8. 95 9. 07 2. 0 2. 0 605 297. 4

N0rE.Ihe calculated values are obtained on the basis of the formula ofAIEMOOH:

a glass vessel which had been flushed with nitrogen sufficiently. Thenthe vessel was weighed. A 1:1 mixture of toluene and n-hexane in anapproximately equal amount to triethylaluminum was added to dilutetriethylaluminum. After the vessel was cooled to -78 C., N-substitutedalkanolamine was gradually added so as to amount to equimol totriethylaluminum. At this time, both react vigorously accompanying heatand gas evolution. After the completion of the addition of all the N-substituted alkanolamine, the whole was further heated to complete thereaction and to give a homogeneous transparent solution. When thereaction liquid was cooled, crystal was precipitated, and after thecompletion of the precipitation, the supernatant liquid was removed bydecantation or by drawing with a syringe, and n-hexane was newly added.The crystal was heated with stirring until it was dissolved in n-hexane.The solution was cooled again to precipitate crystal. After 3 to 5 timesrepetition of this operation for the purpose of purification, thecrystal was dried at a reduced pressure to yield pure crystallinesubstance. Resultant crystals were all colorless in the needle or plateform. The yield was 80 to 90% relative to the theoretical value. Thealuminum content of the resultant crystal was analyzed quantitatively bythe oxine method using 8-oxyquinoline. The quantitative determina- Thesecompounds exist in benzene usually in the form of dimer. When they areused as a constituent of a catalyst, all of the calculation of mol ratiois effected as a monomer. The NMR spectra of these compounds were alsomeasured.

The polymerization of vinyl chloride was carried out by the followingprocess.

A 200 ml. pressure glass reaction vessel'equipped with anelectromagnetic stirrer was flushed with nitrogen, evacuated and cooledto 20 C. Hundred gr. of vinyl chloride and then 5.45 millimole of thereaction product of 1 triethylaluminum and N-substituted alkanolamine(1:1) in toluene were introduced to the vessel. Then with stirring, acompound of transition metal was added to the mixture, so as to give amo] ratio of l/ 3.5 (compound of trransition metal: reaction product).If necessary, further toluene was added so as to make the amount oftoluene in the reaction system constant. In all the runs of theseexamples, the total amount of toluene used was 5 ml. and accordingly thepolymerization was carried out under the condition which could be calledpractically non-solvent polymerization.

The reaction tube was heated to 30 C. and the polymerization wasstarted. The reaction system took gradually the suspension state onaccount of the polymer produced and finally reached the state where anyliquid monomer could apparently be observed. After one hour ofpolymerization, the resultant polymer was processed as in the foregoingexamples, dried to yield white powder polymer which was then weighed.The results are shown in Table 4. In the table, R and R indicate H orthe N- substituent of the catalyst constituent expressed by the generalformula of Al-Et (OCH CH- NRR').

10 EXAMPLES 31 AND 32 VC; nonsolvent; M+AlEt +COCH CHj X (X: C1 or Br)1.22 gr. of triethyl aluminum was dissolved in a liquid mixture of 5 ml.of toluene and 5 ml. of n-hexane, and the resultant solution was cooledto -78 C. 0.7 ml. of

TABLE 4 Polymer Transition Metal Product 01 D638 M.P. Example R, RCompound (gr) (percent) D690 0.) D1

20..- H, CH3 V0013 17. 56.2 1.68 123-125 1, 000 21.; CH CH VOCls..--13.8 56.5 1.62 119-124 980 22.. CH CH T1014 4.3 56.8 1.77 115-119 260 23H, C2H5 V0013 19. 56. 8 1. 66 130435 990 24 2 TiCh 12.5 .56.1 1. 77120-125 330 25.. CzHs, C2115 VOCl; 12. 9 56. 4 1. 63 114-116 1, 180 26.-C5115 OCls 18. 6 56. 6 l. 70 135-139 820 27- CaH C011 VOCl 5.6 56. 0 1.66 123-125 1,100

As evident from theabove-mentioned result, it can be seen that theeffect of N-substituent is great when the reaction product of triehylaluminum and N-substituted alkanolamine (1:1) combined with a compoundof transition metal is used and the catalyst activity is higher in thecase of mono-substituent than in the case of di-substituent.

EXAMPLE 28 VC; M+ (AlEt -N-ethyl-monoethanolamine) Fifty gr. of vinylchloride was introduced at C. in a reaction vessel flushed withnitrogen. 50' ml. of carhon tetrachloride was added thereto and stirred.After 5 minutes later, 2.34 millimoles of the reaction product oftriethylaluminurn and N-ethyl-monoethanolamine (1:1) in toluene and 0.78millimole of vanadium oxytrichloride in toluene were added and thepolymerization was carried out at 30 C. for one hour. 5.5 gr. ofpolyvinyl. chloride was obtained.

In thrs polymerization, when 4.68 millimoles of triethylaluminum, 9.36millimoles of N-ethyl-monoethanolamine and 1.56 millimoles of vanadiumoxytrichloride each in toluene were added to the monomer-in this orderand the polymerization was carried out, 2.3 gr. of polyvinyl chloridewas obtained.

EXAMPLES 29 AND 30 VC; nonsolvent; M+AlEt +HOOH CH CN TABLE 5 PolymerT1014 Product Yield (mmol (gr) (percent) 1e Number: 23? 1. 5 1. 40 16. 730 0. 8 1. 53 18. 2

ethylene chlorohydrin was gradually added and the mixture was heated to50-60" C. to complete the reaction between the both components. Thereacted mixture formed a colorless, transparent solution.

Polymerizations were carried out in the same procedure as in Examples8-19, using a catalyst consisting of 9.60 millimoles of the reactedmixture and 2.40 millimoles of vanadium oxytrichloride.

19.5 gr. of polyvinyl chloride was obtained after the polymerization for1.5 hours at 24 C. This polymer had a M.P. of 145-152 C., a chlorinecontent of 56.6%, D638/D690 of 1.48 and a mean polymerization degree of1400.

Except that ethylene brornohydrin was used instead of chlorohydrin,polymerization was carried out for one hour in almost the same procedureas in the above-mentioned 16.3 gr. of polymer was obtained.

EXAMPLES 3348 VG; solvent; M-l- (AlEtg'MEA) ml. of halogenatedhydrocarbon, a given amount ,of reaction product of triethyl aluminumand monoethanol amine (1:1) and a given amount of a compound of atransition metal, each by themselves or each in the form of benzenesolutions were sealed into separate glass ampoules, respectively. Thesealed ampoules were charged into a 300 ml. autoclave which eifected upand down stirring. The autoclave was closed under the nitrogenatmosphere and then flushed several times with dry nitrogen gas.

The glass ampoules were crushed by nitrogen pressure of ten and oddskg./cm. applied to the autoclave and then the autoclave was heated in anelectric furnace to a given temperature with stirring for 10 minutes.Thereafter, vinyl chloride monomer was introduced under pressure andpolymerization was started under 5 kg./cm. After the polymerization fora given period, the autoclave was cooled. The content was poured intomethanol (which might contain a suitable amount of hydrochloric acid) toprecipitate polymer. After standing over night, the polymer was washedwith methanol, filtered and dried. White powder of polyvinyl chloridewas obtained. The reaction conditions and results are shown in thefollowing Table 6.

TABLE 6 Polymerization Polymer MEA Transition Metal (mmol.) Compound(mmol) Temp.

Example Number Solvent Co (aeach, 2.00 EDG Co (acEMDz, 2.00 EDC 60 10.0Ni (aoaoh, 2.00 EDC 60 10.0 Cr (attach, 2.00 EDC. 60 10.0 Zr (acae)4,2.00 EDG Time Product (1 (gt) DP *ED C: 1.2-diol1loroethane.

EXAMPLES 49-56 VC; solvent; M+ (AlEt -MEA) Polymerizations of vinylchloride were carried out using a catalyst consisting of a reactionproduct between triethyl aluminum and monoethanolamine (1:1) and a com-95 vent was poured into the tube, a compound of transition 30 metal andthe above-mentioned reaction product as a reaction tube equipped with anelectromagnetic stirrer (as in Example 62) was used as a reactionvessel. 100 ml. of 1,2-dichloroethane and a given amount of monoethanolamine or diethanol amine and then given amounts of an organic aluminumcompound and a compound of transition metal, each by themselves or eachin the form of solutions were sealed into separate glass ampoules,respectively. These ampoules were charged into the reaction vessel.

Polymerization and treatment of product were carried out according tothe procedure of Examples 33-48. White powder of polyvinyl chloride wasobtained. The reaction conditions and results are shown in the followingTable 8.

TABLE 8 Polymerization Organo Al Polymer Example Transition MetalCompound Ethanolamine Solvent Press. Temp. Time Product Number Compound(m.mol.) (m.mol.) ml.) (kg/em. C.) (hr.) (gr.)

57 TiCh, 1.73 AlEta, 17 MEA,17 EDC,100... 80 6 10.1 58 TiCla, AlEta, l5MEA, l5 EDC, 100 5 80 6 3.8 Ti(OAC)zCl21 40. AlEtzCl, MEA, 14. EDC, l005 80 6 20.1 i 13,1.42 AlElis, 14 DEA, l4- EDC, 100.. 5 80 6 2.0Ti(0Prz(aeac)2*, 7.88.". AlE 79.- MEA, 70 ECC,100. 5 80 (i 1. 7 620102012, 4.60 AlEta, 10 MBA, 10 EDC,100 2.5 62 e 5.5

*Ti(OP,)z(acac) Titanium diisopropoxybisacetylacetonate.

catalyst component were added in that order. The tube EXAMPLES 63-66 VC;solvent; M-l- (AiEt MEA) +AlEt or AlEt C1 After a ml. pressures glasstube (ampoule) was flushed with nitrogen gas, 20 ml. of1,2-dicho-lroethane, 1.0

50 millimole of vanadium oxytrichloride and a given amount of variousorganic aluminum compounds were introduced lnto the ampoule in thatorder.

Next, the ampoule was connected to a vacuum source TABLE 7 TransitionPolymerization Polymer AlEt Metal Example MEA Compound Solvent Press.Temp. Time Product Number (mmol) (m1nol.) (ml.) (kg./om.z) 0.) (hr.)(gr) DP 5.2 V001 2.3.... EDC,75 2.0 18 3 10.1 1,310

10.0 6102012, 4.6..- EDC, 2.5 32 3 .3 373 10. 0 ClOzClz, 4.6..- EDO, 70-2. 5 32 6 6. 0 432 10. 0 C1O2Cl2, 4.6"-.- EDC, 70 2. 5 32 24 24. 9 1,140

10. 0 CrOQClZ, 4.6. EDC, 70- 2. 5 62 3 7. 7 245 10. 0 0102012,4.6. EDO,70- 2. 5 62 6 12. 2 270 10. 0 0001;, 2.0 EDC, 70- 2.5 62 3 4.4 225 10. 0ClOzClz, 4.6.- recs, 70 2. 5 62 6 2. 2

10. 0 None EDO, 70 2. 5 62 3 0.1

EXAMPLES 57-62 VC; solvent; M+AlEt +a1kanolamine A 300 ml. autoclave ofup and down stirring type (used and 10.6 gr. of vinyl chloride monomerwas Introduced in the pressure-reduced ampoule from a distillationflask. The ampoule was melt-sealed.

Polymerization was carried out at 60 C., for 6 hours,

in Examples 57-61) or a 200 ml. pressure resistant glass with shaking.Treatment of resultant polymer was carried TABLE 9 14 EXAMPLES 76-83VC+vinyl compound; solvent; M+ (AlEt MEA) Copolymerization of vinylchloride with other vinyl compounds were carried out using a solvent.

Number Organic Al Compound Component Polymer Yield (percent) DP productwere used together as in the present Examples 64 66," it was observedfrom analysis of chlorine content, infrared spectrum and nuclearmagnetic resonance spectrum of the polymers that dehydrochlorination didnot occur also in these cases.

EXAMPLES 67-75 VC-l-vinyl compound; non solvent; M+(AlEt -MEA)Copolymerization of vinyl chloride with various compounds were carriedout using, as one component of catalyst, the reaction product betweentriethyl aluminum and monoethanolamine (1: l in almost the same manneras in Examples 8-l9. ml. of comonomer was poured into Vinyl chloridemonomer excepting the Example 67 wherein 10 of comonomer was usedinstead of 5 ml. In them case of block copolymeriza'tion, ahomopolymerization of vinyl chloride was at first carried out for agiven period, andthen the polymerization vessel was cooled to C. againto add a comonomer and to extend the polymer chain by copolymerization.

The results obtained are shown in the following Table 10.

A given amount of 1,2-dichloroethane was poured into a 200ml. pressureresistant glass reaction tube equipped with an electro-magnetic stirrerafter flushing the tube with nitrogen gas. Vinyl chloride monomer wasdissolved in this 1,2-dichloroethane under pressure and was driven off.Next, given amounts of a catalyst and a comonomer were added into thetube with stirring, and the tube was closed.

Vinyl chloride was introduced under pressure with stirring andpolymerization was carried out under conditions of given pressure,temperature and period.

After completion of the reaction, methanol (which might contain asuitable amount of hydrochloric acid) was poured into the reactionliquid, polymer being precipitated. Resultant polymer was washed withmethanol, filtered and dried at C. in vacuo for 24 hours. The polymerwas white powder. The reaction conditions and results are shown in thefollowing Table 11 below.

The unit of vinyl acetate, methyl acrylate or ethyl vinyl ether presentin the copolymers of the present Examples 7683 was confirmed frominfrared spectrum. The comonomer contents in the copolymers werecalculated from analytical value of chlorine.

TABLE 10 Acetone Extraction Polymerization AlEt Transltion .Al/TlPolymer Soluble Insoluble MEA etal (molar Temp. Time Product (Weight(Weight (mmol) Compound ratio) Comonomer 0.) (hr.) (gr.) prcent)percent) 4, 75 3.12 Cetylvinyl ether 26 2 11.2 14.7 85. 3 5. 3. 12 Vinylacetate 23 1 13. 9 32. 2 67. 8 4.75 3.12 Isobutylvinyl ether- 23 2 15.14. 3. 12 .-d0 23 2+2 8. 4.75 3.08 Vinyl acetate 23 0.5+2 17. 4.75 3.12Maleic acid 23 2 14. 4.75 3.04 do 27 2 30. 4.75 3.08 .do- 27 0. 3+2 24.9.50 3.08 Styrene" 27 0. 5+2. 5 19.

' As seen in the table, in the cases of block copolymerizations, thepolymerization times are indicated in two steps; homopolymerization andcopolymerization.

The presence of comonomer unit was confirmed from infrared spectrum, inboth the acetone-soluble parts and acetone-insoluble parts of thepolymers in the cases of EX- amples 68, 69 and 71, and in theacetone-insoluble part of the polymer in the case of Example 67.

EXAMPLES 84-98 Copolymerizations of vinyl chloride with olefins werecarried out using such a ctalyst system as in Examples 84-90, consistingof a compound of transition metal, triethyl aluminum andmonoethanolamine, each in a given TABLE 11 Polymerization GopolymerTransition Comonomer Metal Content Compound Solvent Comonomer Press.Temp. Tim (mol (mmoL) (ml.) (g (kg./cm.2) 0.) (hr.) percent) V0013, 2.3EDC, 75-.-. Vinylacetate, 2.8 2.0 30 2 3. 3 V0013, 2.3. EDC, 2. 6 3O 227. 0 CrOzGlz, 4 EDC, 75 2. 5 32 3 3. 0 CrO2Ol2, 4 EDC, 75 2. 5 32 6 8.6C1O2C12,4 EDC, 75 2. 5 32 s 23. 0 0102012, 4. EDC, 75 2. 5 32 6 36. 3CrOzClz, 4.6..- EDC, 75 Ethyl vinyl ether, 5 2. 5 32 6 3. 1 CI'OzClz,4.6--- None Vinyl acetate, 46.7.-. 2. 5 32 9 34. 8

15 16 amount, or such a catalyst system as in Examples 9l98, sultantfiltrate was poured into thrice its amount of methconsisting of acompound of transition metal and the reanol, and allowed to stand for 4hours. After the resultant action product between triethyl aluminum andmono precipitate was lltered, the filterad polymer was dried inethanolamine (1:1). A 300 ml. autoclave of up and down vacuo at 40 C.for 24 hours. stirringtype w-as used.

The copolymerization was carried out in the presence of EXAMPLE 99 100ml. of 1,2-dichloroethane as a polymerization sol- VC+CC12=CHCh Solvent;M,+(A1Et3 MEA) vent, at a total pressure of 10 kg./cm. in which partialPressure of Vinyl chloride was 5 and that of 70 ml. of trichloroethylenewas poured into a 200 ml. Olefin g was kgv/cttl-z, at a glvehtemperature and pressure resistant glass reaction tube equipped with aha 8 Y P 0f h In Examples the electromagnetic stirrer, after flushingwith nitrogen gas. Polymerllatlon was earned out at first at for 2 Next,4.6 millimole of chromyl chloride and 10.0 millihours and then at 130 C.for 4 hours. mole of the reaction product between triethyl aluminum- Thereaction conditions and results are shown in the and monoethanolamine(1:1) were added thereto in that following Table 12. order, and the tubewas closed.

TABLE 12 Polymerization Copolymer Coinonoiner Example Transition MetalAlE T3 MEA Temp. Time Product M.P. content Number Compound (mmoL) (mmoL)(mm0l.) Comonomer 0.) (hit) (gr) C.) P (molpercent) lCla, 1.5. TKOACMCE,1.5 Tlch, 1.5

VOCla,1-5 l5 15 91 'liClg, 1.5 AlEtg-hlEA (mmol.), l5

92 V001 1.5 AlEtg-MEA (mmol.), 15...

' AlEti-MEA (mmol.), 15... AlEta-MEA (mmol.), 15 AlEtJg-MEA (mmol.), 15AlEta-MEA (mmol.), 15...

97 CX'O2C12, 4.6.---

AlEta-MEA (mmol.), 10... 9s 0102012, 4.6 AlEta-l\1EA(nunol.),10-.

Infrared spectra of the polymers obtained in Examples After the nitrogengas in the tube was replaced by vinyl 91 and 94 were compared with thatof the homopolymer chloride, vinyl chloride was charged under pressurewith of vinyl chloride. It was observed that the absorption stirring,and polymerization was continued for 6 hours bands of 688 cm. and 635cm.- in the spectrum of the at 2.5 kg./cm. and 32 C. The product wastreated as homo olymer of vinyl chloride changed to those of 683 inExamples 33-48 and 1.2 gr. of polymer was obtained.

cm. (shift), 635 cm.* (intensity is reduced) and 751 The result ofelementary analysis was as follows. C: cm. (new absorption) in thespectrum of the vinyl 33.8%, H: 4.1%, Cl: 60.5%.

chloride-ethylene copolymer of Example 91, and to those It was confirmedfrom the above-mentioned chlorine of 683 cm.- (shift) and 635 cm.-(intensity is reduced) content that vinyl chloride-trichloroethylenecopolymer in the spectrum of the vinyl chloride-propylene copolymercontaining 8.06 mole percent of trichloroethylene was of Example 94. Itwas further observed that the spectrum formed.

of the vinyl chloride-propylene copolymer had a new EXAMPLES 100406absorption band at 1381 cm? which was absent in the case of homopolymerof vinyl chloride. VDC; solvent; M+( 3' A180, the magnetic resonancespectra of the Polymerization of vinylidene chloride was carried out PQObtalhed 1h Examples 91 and 94 were Compared using as catalyst, 5.0millimole of the reaction produce Wlth that Of homopolymer of Vinylchloride- It w between triethyl aluminum and monoethanolamine (1:1)Served that as for the signals of P y y chloflde, and 2.5 millimole ofvarious compounds of transition a multiplet (CH) around 7:5.61 and amultiplet (CH l, f intensities in the Part, of higher 70 ml. of1,2-dichloroethane was introduced into a 200 magnetic field sideincreased, whereas those in the part m1. pressure resistant glassreaction tube equipped with of lower magnetic field side decreased inboth the vinyl a n electroma netic t e stirrer, after flushm withnitro-- chloride-ethylene copolymer obtained in Example 91 and gm gas.Nexgt a cogpound of transition mgetal and, the

the vinyl chloride-propylene copolymer obtained in Examabovemlentionedreaction product were added in that ple 94. This fact evidently showsthat many units of vinyl order Finally 10 mL of vinylidene ch10 ri de(0125 mole chloride ad asent to a unit of olefin exist in the polymer121 gm) was added and the tube was closed Reactim;

.chaih and is a Proof of the fohhahoh of copolymer It was carried out ata given temperature and for a given 15 also confirmed from the Poslhohsof the slghals of period of time. After completion of the reaction,methaethylene unit or propylene unit appearing in the spectra of H01(which might contain a Suitable amount of hydro h polymers that not amixture of polyvinyl ch and chloric acid) was added to the reactionliquid to precipi- Polyolefin but a collhlylher 15 formed; tate thepolymer. After allowed to stand over night re- In the present examples,the separation and purification sultant polymer was filtered Washed withmethaholand of resultant copolymer of vinyl chloride with olefin weredried at 0 c in vacuo for 24 hours h polymers were carried u as f0 whitepowder, the infrared spectra of which accorded Raw P y was added to 20times its amount of tetracompletely with those of a radicalpolymerization product hydrofuran and extracted at room temperature for12 having good purity. The majority of white polymers prohours, Afterinsoluble polyolefin was filtered off, the redu ed using other modifiedZiegler ataly t ha been found from infrared spectrum to contain in theirpolymer molecule chains such an irregular structure as seen inchlorinated polychloroprene or the like, on account ofdehydrochlorination and various reactions accompanied. However, theabove-mentioned fact cannot be seen in the polymers obtained in thepresent examples.

The reaction conditions and results are shown in the following Table 13.

VDC; solvent; M+AlEt +MEA 5.0 millimole of triethyl aluminum and 5.0millimole of monoethanolamine were separately added to the reactionsystem, instead of the reaction product between triethyl aluminum andmonoethanolamine (1:1) used in Example 101. Other conditions inpolymerization were the same as those in Example 101. 2.1 gr. of whitepolymer was obtained.

EXAMPLES 10 8-111 VDC; solvent; M+(AlEt -MEA) (various amounts ofcatalyst and VDC) In the present examples, polymerizations were carriedout in the same way as in Example 101 which the catalyst system (Al/V=2)consisting of the reaction product between triethyl aluminum andmonoethanolamine (1:1) and vanadium oxytrichloride (polymerization: 60C., 3 hours) was used except that the amount of the catalyst and theamount of vinylidene chloride (VDC) charged were varied. In the examplesin which the amount of the monomer was varied, the amount of1,2-dichloroethane as a solvent was adjusted so as to give the totalamount of the system consisting of solvent, monomer and catalyst, 85 ml.The reaction conditions and results are shown in the following Table 14.The polymers were all white powder.

TABLE 14 VOGl VDO Polymer Monomer Yield (mmoL) Feed (1111.) (percent)Example Number:

EXAMPLES 112-115 VDC; solvent; M-l-(AlEt -MEA) (Various solvents)Polymerizations were carried out in the same way as in Example 101,except that various solvents were used instead of 1,2-dichloroethane.The amounts of the solvents were all 70 ml. Resultant polymers were allwhite powder. The solvents and results are shown in Table 15.

18 EXAMPLE 116 VDC; solvent; M-l-(AlEt -N,N-Ph -MEA) Polymerization wascarried out in the same way as in Example 101, except that a reactionproduct between triethyl aluminum and N, N-diphenyl monoethanolamine1:1) was used instead of the reaction product between triethyl aluminumand monoethanolamine (1:1) used in Example 101. 2.11 gr. of polymerhaving a pale light blue color was obtained (yield: 17.3%).

EXAMPLE 117 VDC; non solvent; M+(AlEt -MEA) 2.0 millimole of thereaction product between triethyl aluminum and monoethanolamine (1: 1),1.0 millimole of vanadium oxytrichloride and 8 ml. of vinylidenechloride were introduced in that order, under cooling, into a 18 ml.pressure resistant glass reaction tube, after flushing with nitrogengas. The tube was sealed, and then non-solvent polymerization ofvinylidene chloride was carried out with stirring, at 60 C., for 3hours. The treatment after completion of the reaction was the same as inExample 101. 4.45 gr. of white polymer was obtained (yield: 45.7%

EXAMPLES 118-123 VDC+VC; non solvent; M+ (AlEt -MEA) 2.0 millimole ofthe reaction product between triethyl aluminum and monoethanolamine(1:1), 1.0 millimole of vanadium oxytrichloride, a given amount ofvinylidene chloride and a given amount of vinyl chloride were introducedin that order, under cooling, into a pressure resistant glass reactiontube, after flushing with nitrogen gas. The tube was sealed, and thennon-solvent copolymerization of vinylidene chloride with vinyl chloridewas carried out at 60 C., for 20 hours, with stirring. The treatmentafter completion of the reaction was the same as in Example 101. Powderypolymer was obtained. The polymer was dissolved in tetrahydrofuran,filtered and reprecipitated from distilled methanol for the purpose ofpurification. Thus purified polymer was used for samples for elementaryanalysis, infrared spectrum and nuclear magnetic resonance spectrum.

The results are shown in the following Table 16.

*VC: Volume at 78 C.

. The contents of vinyl chloride component in the copolymers werecalculated from the analytical values of chlorine. The absorption banddue to the deformation vibration of CH in vinyl chloride unit can beseen clearly at 1205 cm: in every infrared spectra, (measured by the KBrtablet method), of the polymers obtained in Examples 118-123. Since thisabsorption. band is not found in polyvinylidene chloride and is supposedto appear at 1250 cm.- in polyvinyl chloride, the above-mentioned resultshows that the samples are not a mixture of homopolymers but copolymers.(Reference: J. Polymer Sci., A3, 3919 (1965)). Nuclear magneticresonance spectra of the samples were measured at C. from 10%chlorobenzene solutions thereof.

EXAMPLES 124-127 VDC+vinyl compound or olefin; nonsolvent; M+ (AlEt-MEA) 2.0 millimole of the reaction product between triethyl aluminumand monoethanolamine (l 1), 1.0 millimole of 19 vanadium oxytrichloride,4.0 ml. of vinylidene chloride and 4.0 ml. of a specific comonomer wereintroduced in this order, under cooling, into a 18 ml. pressureresistant 20 5. A method for polymerizing at least one vinyl compoundexpressed by a general formula of X glass tube, after flushing withnitrogen gas. The tube was sealed, and then non-solventcopolymerizations of vinyl- OHi-O idene chloride and several kinds ofvinyl compounds were 01 carried out at 60 C. for 20 hours with stirring.The wherein X is a member selected from the group consisttreatmentsafter completion of the reaction were the same ing of hydrogen andchlorine atom, which comprises as in Example 101. White powder ofpolymer was obpolymerizing said vinyl compound by the use of amoditained. The polymers were extracted with acetone or tetrafiedZiegler type catalyst consisting of (a) a compound of hydrofuran for 8hours, or using successively the one of a transition metal, (b) anorganoaluminum compound the above-mentioned for 8 hours and then theother for and (c) a lower aliphatic alcohol having, as a substituent, 8hours (total: 16 hours) and reprecipitated from distilled a memberselected from the group consisting of an amino methanol for the purposeof purification. Thus obtained radical, nitrile radical and a halogenatom, in the presence polymers were used for the samples for elementaryanalof a solvent the molar ratio of said alcohol component 'ysis andinfrared spectrum. (0) to said organoaluminum component (b) being withinThe results are shown in the following Table 17. the range of about 0.5to 2.

TABLE 17 Solvent Extraction Comono- Oomonomer in mer in ComonomerAcetone Acetone in THF Acetone Soluble Acetone Insoluble THF SolubleSoluble Fraction Insoluble 9 Fraction Soluble Fraction Example (weight(mol (weight (mol (weight (mol Number Comonomer percent) percent)percent) percent) percent) percent) Propylene b X X X X 90. 6 65. 0Vinyl Acetate. .9 66. 2 21. 5 33. s 15. 3 X X Me methacryla .0 75.2 50.824.8 27.0 X X Me acrylate 94.1 99. 8 45. 9 0.0 X X X a Feed volume: 4.0ml. at 78 0. b X-Not extracted.

9 The whole amounts of Acetone Insoluble Fractions oi No. 125-126 wereTHF Soluble.

The contents of comonomer in the copolymers were 6. A method accordingto claim 5, wherein said solvent calculated from the analytical valuesof chlorine. It was is a halogenated hydrocarbon.

confirmed from the infrared spectra carried out by the KBr tablet methodand from the solubilities in acetone or tetrahydrofuran of the polymersthat the polymers were the copolymers of vinylidene chloride and aspecific comonomer.

What is claimed is: 1. A method for polymerizing at least one vinylcompound expressed by a general formula of /X CH2=C wherein X is amember selected from the group consisting of hydrogen and chlorine atom,which comprises polymerizing said vinyl compound by the use of amodified Ziegler type catalyst consisting of (a) a compound oftransition metal, (b) an organoaluminum compound and (c) a loweraliphatic alcohol having, as a substituent, a member selected from thegroup consisting of an amino radical, nitrile radical and a halogen atomthe molar ratio of said alcohol component (c) to said organoaluminumcomponent ,(b) being within the range of about 0.5 to 2.

2. A method according to claim 1, wherein said compound of a transitionmetal is selected from the group consisting of halides, oxyhalides,alkoxides, alkoxyhalides, alkoxyacetylacetonates, acetoxyhalides andacetylacetomate of titanium, vanadium, chromium, iron, cobalt, nickel,zirconium and manganese and TiCl /aAlCl 3. A method according to claim1, wherein said organoaluminum compound is selected from the groupconsisting of compounds expressed by a general formula, AlR X wherein Ris a radical selected from alkyl, cycloalkyl and aryl radical, X is ahalogen atom and m is selected from 3, 2, 1.5 and 1.

4. A method according to claim 1, wherein said lower aliphatic alcoholis selected from the group consisting of alkanol amines and compoundsexpressed by a general formula of HOCH CH X wherein X is selected fromthe group consisting of Cl, Br atom and CN radical.

7. A method for polymerizing at least one vinyl compound expressed by ageneral formula of wherein X is a member selected from the groupconsisting of hydrogen and chlorine atom, which comprising polymerizingsaid vinyl compound by the use of a modified Ziegler type catalystconsisting of (a) a compound of a transition metal, (b) anorganoaluminum compound and (c) a lower aliphatic alcohol having, as aconstituent, a member selected from the group consisting of an aminoradical, nitrile radical and a halogen atom, in the absence of a solventthe molar ratio of said alcohol component (c) to said organoaluminumcomponent (b) being within the range of about 0.5 to 2.

8. A method for polymerizing at least one vinyl compound expressed by ageneral formula of CH2=O wherein X is a member selected from the groupconsisting of hydrogen and chlorine atom, which comprises polymerizingsaid vinyl compound by the use of a catalyst consisting of a compound ofa transition metal and an isolated reaction product between anorganoaluminum compound and an alkanolamine.

9. A method for polymerizing at least one vinyl compound expressed by ageneral formula of wherein X is a member selected from the groupconsisting of hydrogen and chlorine atom, which comprises polymerizingsaid vinyl compound by the use of a catalyst consisting of a compound ofa transition metaland an isolated reaction product between anorganoaluminum compound and an alkanolamine in the presence of a freeorganoaluminum compound further added the molar ratio of saidalkanolamine to said organoaluminum component being within the range ofabout 0.5 to 2.

10. A method for copolymerizing at least one vinyl compound expressed bya general formula of wherein X is a member selected from the groupconsisting of hydrogen and chlorine atom, and a polymerizableunsaturated compound, Which comprises copolymerizing said compounds bythe use of a modified Ziegler type catalyst consisting of (a) a compoundof a transition metal, (b) an organoaluminum compound and (c) a loweraliphatic alcohol having, as a substituent, a member selected from thegroup consisting of an amino radical, nitrile radical and a halogen atomthe molar ratio of said alcohol comwherein X is a member selected fromthe group consisting of hydrogen and chlorine atom, and a polymerizableunsaturated compound, which comprises copolymerizing said compounds bythe use of a catalyst consisting of a compound of a transition metal andan isolated reaction product between an organoaluminum compound and analkanolamine the molar ratio of said alkanolamine to saidorganoaluminurn component being within the range of about 0.5 to 2.

References Cited UNITED STATES PATENTS 2,932,633 4/1960 Juveland et al260-94.9 3,196,137 7/1965 Cain 26092.8 XR 3,219,648 11/1965 Hill260-94.9 XR 3,251,810 5/1966 Biining 26078.5

FOREIGN PATENTS 620,226 5/1961 Canada.

JOSEPH L. SCHOFER, Primary Examiner I OHN KIGHT, Assistant Examiner US.Cl. X.R.

